Emulsion



Patented July 11, 1933 BENJAMIN R. HARRIS, OF CHICAGO, ILLINOIS EMULSION No Drawing.

My invention relates in general to improved emulsions and particularly a margarine emulsion of an improved nonspattering type. The present application is a continuation in part of my prior application, Serial No. 481,349,

filed September 11, 1930. The latter application is a division of application Serial N 0.

475,622, filed August 15, 1930 as a continuation in part of application Serial No. 383,143, 13 liled August 2, 1929.

By means of my invention in whichcertain novel products are incorporated into the margarine emulsion, I impart superior qualities to the margarine, giving it many advantages and improvements which have not been possible heretofore. T hose skilled in' the art are referred to my co-pending application, Serial No. 566,156 filed September 30, 1931, as a continuation in part of application Serial No. 475,622. In general the present invention represents a specific embodiment of the main invention disclosed in my co-pending application above referred to, and while the preseut disclosure is substantially complete in so far as it describes the invention andsupports the claims, those interested in the art are referred to the co-pending case for a more complete disclosure of the basic. concept of the invention.

The principal object of my present invention is to improve such forms of emulsion as margarine.

Another object is to reduce the spattering of margarine when used for frying purposes and generally improve its frying behavior.

Other objects and features of the invention will be apparent from a consideration of th following detailed description,

As was disclosed in my prior applications I have discovered a large class of chemical compounds which may be used to impart improved characteristics to all types of wateroil emulsions, particularly those used for cooking purposes, and other types of culinary fat preparations. These substances have several characteristics 'in common which make them very valuable in their use with margarine. These substances are compatible with mild acids and in particular with lactic acid in the concentration and under the conapplication filed September 30, 1981. Serial No. 566,160.

ditions existing in margarine. They are in general difiicultly soluble in oils and fats and aqueous media and in many cases are substantially insoluble. Most of these compounds may be used in very small quantities, as they may be considered to concentrate at the water-oil interface of the emulsion rather than be freely dissolved in either the water or oil phase. These substances are' semi-colloidal or truly colloidal in character and are frequently colloidally dispersible in aqueous and/or oleaginous media. They are, moreover, substantially non-volatile at margarine frying temperatures and so will" remain in the margarine and perform their function during frying.

One of the most important characteristics of these compounds is the presence in the molecule of two types of groups in balanced relation to each other, one group being'hydrophyllic and Water wetting in character, and the other group being lipophyllic or fat wetting in character. These groups must exist in the molecule in such a state of balance that they will function at the water-oil interface in the intended manner. Presumably these substances orientate themselves at the interface, by reason of the balance of the two types of groups, but it is understood that the invention does not depend upon this explanation.

My prior application treats exhaustively of the manner in which the balance between the two groups may be determined so that without tests of any kind it is possible for the skilled colloid chemist to pick out compounds which can not function effectively as anti-spatterers, as well as compounds which clearly will be effective as anti-spatterers.

However, there are some compounds of 90 such character that the state of balance existing between the two groups in the mole-. cule may be doubtful, and the balance in these cases is preferably determined by a simple quick test.

hydrophile-lipophile The balance of the groups in the compounds which I apply in my invention is one of the characteristics and determinants of the class of substances which I employ.

The test which I have chosen as a means for determining the hydro bile-lipophile balance in organic compoun I call the spoon test. It is carried out as follows 2 From 0.05 for the general the following:

. are then introduced in small portions into the mortar and macerated thoroughly with the paste first prepared until the entire ten gram portion is thoroughly-and uniformly intermixed with the material in the mortar. Two grams of this mixture are introduced into a tablespoon and held directly over a free flame such, for example, as a Bunsen flame, one or two inches long in such a position that the point of the flame just about reaches the bottom of the spoon. A clean sheet of paper is placed on the bottom of the burner by inserting the stem of the Bunsen burner prior to lighting through a hole made in the center of the paper and allowing the paper to drop to the base of the burner to catch the margarine splashed out during the heating. The mixture in the spoon is heated until all of the water has been boiled ofi and ebullition ceases and the spots on the paper observed. I a

If this treated margarine spots the paper to the same extent as the untreated margarine from which the former was prepared, then the lipophile and hydrophile groups of the compound are not balanced. The number and size of spots on the paper or the added weight can be readily determined.

If the increase in weight of the paper or the number and character of the spots .produced on the paper up until all the water has boiled off are less than that produced by similarly heating two grams of the original untreated margarine employed for the test,

than the material or substance in questionhas balanced hydrophile-lipophile groups.

The expression balanced lipophile and hydrophile groups used in the claims is to be interpreted in terms of the above described spoon test, as well as in the light of the entire. disclosure.

My present invention relates to a class of substances of the general character described in my co-pending application. These substances which I claim herein are all sulphonic acid derivatives and have certain characteristics in common, as the following description will establish. Among the sulphonic acid derivatives which I have used successfully as anti Spattering agents, either in relatively pure form or admixed with other unobjectionable materials, and which may be used improvement of emulsions are Na Monostearine sulphoacetate (sodium salt) Na Palmityl sulphoacetate godium salt) 0 l CHr-(CHfln-CHx-O--CHa-SfiO ONa Cholesteryl sulphoagetate salt) CnH4 O!3CHz-S O OK Palmityl sulphopropionate (sodium 52118 0 Ha ONa Palmltyl sulphonic acid (sogium salt) Na Ceryl sulphonic acid (sodium 62111;)

CHPCHPCHPS=O In the case of the compounds indicated directly hereinabove, the hydrophile sulphonic acid group dominates and is inadequately balanced by the lipophile group, that is, the lipophile characteristics of the latter are too weak to balance and co-act with thesulphonic acid group.

Generally speaking I select for mylipophile grou radicles of relatively hi h molecular weig t. For example, the ollowing material may be utilized as sources of lipooleic acid, lauric acid, palmitic acid, lauryl alcohol, cholesterol, monostearyl glycerine (monostearine, so called), many higher molecular weight esters with esterifiable hydroxy groups and other substances with marked afiinity for oils and fats, as pointed out more fully in my co-pending application Serial No. 566,156.

In general, I use relatively small propor-,

tions of the anti-spattering agents, up to 2% and in some instances, as little as .1%,- or

methods Is the preparation of palmityl sulless, but sufficient to improve the frying behavior of the margarine; however, larger proportions may be used if desired.

I do not by any means restrict-the use of these anti-spattering agents to margarine, inasmuch as they have many useful colloidal properties and can function as wetting, detergent, penetrating, emulsifying, frothing and foamingagents in the arts where suchmaterials are employed. In fact, even in margarine, they function in other ways than merely to improve the frying characteristics. One of these additional improvements is that the margarine is much less likely to leak and suffer from so-called weeping by virtue of the fact that the antispattering agent improves the emulsion in such-a way that the aqueous phase is much more tenaciously held in the margarine than otherwise.

Numerous methods are available for the introduction of the sulphonic acid group. In the case of aromatic sulphonic acids, of course, the standard sulphonation procedures employed for producing aromatic sulphonic acids may be used and if desired, the lipophyllic group may be introduced subsequent- In the case of aliphatic sulphonic acids, and for that matter, even for the production of aromatic sulphonic acids, a reactive halogen may be caused to react with sodium sulphite or potassium sulphite or ammonium sulphite or some other sulphite in aqueous solution, if desired. 7

Another method is tointroduce a sulphhydryl or disulphide or some other suitable sulphur group and then oxidizeto'the sulphonic acid with nitric acid or a permanganate or some other oxidizing agent.

As an example of one of these methods, I describe herewith the preparation of the sodium salt of cholesteryl sulphoacetate; nine parts of cholesterol, nine parts of brom acetyl bromide, and forty parts of benzene were heated under a reflux condenser for two' hours at the boiling point of the mixture. The reaction mixture was then washed repeatedly with hot water until it was substantially free of acid and freed of benzene by distilling from a steam bath. Seven parts of this reaction produce were then treated with seven parts of sodium sulphite, Nasm), dissolved in forty parts of hot water, for five hours at the temperature of boiling water and with continuous, vigorous agitation. This reaction mixture was washed several times with hot brine until free of sulphites, dried and finally purified by extracting the impurities with dry ethyl ether. Analysis showed that the product was the sodium salt of cholesteryl sulphoacetate in relatively pure form, with an-admixture of sodium chloride.

An illustration of another one of these phonic acid, (sodium salt), which I prepared as follows:

I treat twenty five parts of palmityl mercaptan with a hot solution of fifty parts of, potassium permanganate in eight hundred parts of water at a temperature of approximately 95, adding the permanganate solution in four successive portions with stirring to avoid too violent a reaction. The mixture is heat'ed at 100 C. for three hours and the remainin potassium permanganate is reduced wit oxalic acid but not in excess.

The mixture is filtered hot and the manganese dioxide is washed with hot water. The filtrate and washings are cooled and filtered at 40 to remove oily impurities.

On cooling and salting out with sodium chloride, the potassium salt of palmityl sulphonic acid separates out.

Of course, I do not limit myself to the above described methods of preparing these anti-spatterers, nor to the particular substances mentioned above, which are merely v illustrative embodiments of my invention. Aromatic as well as aliphatic sulphonic acids may be employed to furnish hydrophyllic groups.

My emulsionimproving substances may be represented by the structural formula in which R? is a lipophile radical of relatively higher molecular weight, S represents sulphur linked to carbon, 0 stands for oxygen, X stands for innocuous cations, and 'w is a whole number. The lipophile radical may be an ester group of higher molecular weight, while the hydrophile portion of the molecules represented may include preferabl a sulphoacetic acid group.

Among t e most satisfactory of compounds ample, that when from one tenth to one half per cent of sodium monostearme sulphoacetate is added to margarine in a suitable manner, spattering is almost entirely prevented, and other improvements secured. In the general consideration of all of these substances it is to be noted that the hydrophile group is at or near an end of the molecule.

It must not be inferred from the preceding part of this specification that every antispattering substance of the character herem disclosed must be insoluble in oleaginous and/or aqueous media. It is true that the greater number of anti-spatter-ing compounds of the present invention are substantially insoluble in these media, but there are a limited number of water solublecompounds which, if used in sufiiciently larger proportions may have an effect in-reducing spattering during frying.

It appearsthat in a given homologous series there is a point or range at or within which-lipophile and hydrophile characteristics are so balanced that an optimum power for the prevention of spattering is imparted to the molecule. Going from this point, higher in the series, in-the direction of increasing molecular'weight in the lipophile group with a given sulphonic radicle as the hydrophile group, the anti-spattering power diminishes because of excessive llpophile characteristics in the molecules; going down from this point or range, lower in the series, anti-spattering power again diminishes because of excessive hydrcphile characteristics in the molecules; the tendency to dissolve in water concurrently increases and the emulsifying value in general also decreases. This is not, however, to be taken to signify that a water soluble substance cannot function as an anti-spatterer. Examples of water soluble anti-spatterers are:

Sodium butyl sulphonate orn-cm-om-oHr-s-om Octyl sulphoacetate (sodium salt) Butyl-diethylene glycol sodium sulphoacetate CHrCHz-CHg-CHz-O-CHz-CH In general it is true that, other things being ly large number of carbons in the lipophile group. However, below ten or twelve carbons, for example, the tendency for solubility in water gradually increases and in the range, four to seven or eight carbons, the anti-spatterers are generally rather freely soluble in water. Below four carbons, almost invariably, the lipophile group is too weak to balance the hydrophile group and anti-spattering power is absent. It is evident, therefore, that the total number of possible, freely water-soluble anti-spatterers is necessarily small as compared with the but they have a particular adaptation for use with all culinary emulsion products such as margarine. Commercial margarine after being treated with my anti-spattering agent, when fried in a shallow pan exhibits improved frying behavior in that it allows its water to boil 01f quietly, frys in a pleasing and comparatively quiet' manner with the formation of considerable turbid froth and foam after the manner of butter, reduces the tendency of the curd to stick to the bottom of the frying pan and reduces the amount of material which escapes from the pan by spattering. Untreated margarine on the other hand when fried bump's' turbulently, sputters noisily and foams comparatively little.

Also what little foam there is is transparent and of an entirely different character from that obtained from margarine previously treated with an anti-spatterer.

My emulsion improvers may be introduced into the margarine in a number of ways, as long as a satisfactory dispersion is obtained. For instance, the-main constituents of margarine are edible oils and fats and cultured milk, and the anti-spattering or improving compounds may be introduced either into the oils or milk in any suitable manner. They may also be introduced into the churn during the production of the emulsion in its liquid state, care being taken'to bring about the necessary dispersion. Or, the anti-spattering material may be used in a dry condition and mixed with the salt which is worked into the crystallized margarine, or the antispattering material may be made into a paste with milk, and kneaded into, or blended into the margarine.

As to the specific application of the invention to margarine and other emulsions or oleaginous culinary preparations, it is clear that since there are many sulghonic acid derivatives containing balanced ydrophile and lipophile groups, t is impractical and un necessary to list each particular combination of groups which can be used in accordance with my invention. Moreover, while I leave somethingto the skill of persons a plying my invention, my description is who 1y sufiiciently exhaustive, particularly when considered with respect to my prior applications, to enable those skilled in the art to successfully practice the same.

The term non-spattering margarine as used in the claims, is employed to desi ate a margarine, the frying behavior of whlch is improved by the addition thereto of the novel materials of my invention herein described to reduce spattering. Margarine is used in the sense in which this term is employed vin the U. S. Revised Statutes, including the recent Haugen amendment, extending the meaning of the term for tax purposes to Include substances not emulsified with cultured 25 milk.

What I claim as new and desire to protect by Letters Patent of the United States is: V

1. A non-spattering margarine including an oleaginous material and an aqueous material, and having included therein a proportion of an improving agent comprising a chemical substance characterized by a coaction in its molecule of'ba'lanced lipophile and hydrophile groups and represented by the formula n'li=o x in which R is a lipophile radical, S- re resents sulphur linked to carbon, 0 stan s for oxygen, X stands for innocuous cations, and w? is a whole number, at least one. a

2. A non-spattering margarine including oleaginous material and aqueous material, and having included therein a proportion of a chemical substance characterized by a coaction in its molecule of balanced lipophile and hydrophile groups and represented by the formula o n-Lo in which R is a lipoghile radical comprising an ester group, represents sulphur linked to carbon, 0 stands for oxygen, X stands for irmocuous cations, and w is a small whole number.

3. A non-spattering margarine including oleaginous material and aqueous material and having included therein a proportion of a carboxylic ester of sulphoacetic acid, hav- :ing balanced lipophile and hydrophile groups. p p

4. non-spattering margarine including oleaginous material and aqueous material and havmg included therein a pro ortion of an ester of sulphoacetic acid, w erein the sulphonic group is balanced by a lipophile group, and wherein the lipophile function is exercised primarily by acyl groups.

5. non-spattering margarine includin oleaginous material and aqueous materia and having included therein a proportion of an ester of sulphoacetic acid, wherein the sulphomc group is balanced by a lipophile group, and wherein the lipophile function is exercised primarily by at least one stearyl group. a

6. A n0n-spattering margarine including oleaginous material and aqueous material,

and having included therein a proportion of' a salt of monostearine sulphoacetate.

7. A non-spattering margarine including oleaginous material and an aqueous material and having included therein a proportion of the sodium salt of monostearine sulphoace-' tate.

. 8. A non-spattering margarine including in which R is a relatively high molecular weight alkyl radical, S represents sulphur linked to carbon, O stands for oxygen, .X stands for innocuous cations, and w .is a whole number, at least one.

10. An improved non -spattering margarine emulsion, having an oleaginous phase and an aqueous phase, and including a proporition of sodium salt of palmityl sulphonic ac1 11. A'non-spattering margarine including an oleaginous material and an aqueous material and having included therein a proportion of a chemical substance characterized by a co-action in its molecule of balanced lipophile and hydrophile groups and represented by the formula [RF-3:01)! (i 10 in which R is a lipophile radical, S

repreisents sulphur linked to carbon, 0 stands for oxygen, X stands for innocuous cations, and w is a Whole number at least one, said substance-being substantially nsoluble in oleaginous and aqueous media,

substantially non-volatile at Water boiling temperatures, and Compatible with m ld 4 acids.

12. A non-spattering margarine including oleaginous material, and an aqueous material and having included therein a proportion of a chemical substance characterized by a co-action in its molecule of balanced lipophile and hydrophile groups and represented by the formula in which R is a lipophile radical comprising an ester grou S reprsents sulphur linked to carbon, stands for oxygen, X stands for innocuous cations, and w is a small whole number, said substance being substantially insoluble in oleaginous and.

substance having balanced hydrophile and gr lipophile groups, in which the hydrophile function is imparted to the molecule primarily by a sulphonic acid radical, and in which the lipophile group is in the form of an ester of a fatty 'aci 15. A non-spattering margarine including an oleaginous material and an aqueous material, and having included therein a propor tion of an improving agent comprising a water soluble substance characterized by a coaction in its molecule of balanced lipophile and hydrophile groups and represented by the formula Rd =O x L w in which R is a lipophile radical having at least four carbon atoms, S represents sulphur linked to carbon, 0 stands for oxygen, X stands for innocuous cations, and w is a whole number, at least one.

16. A non-spattering margarine, having an oleaginous phase and an aqueous phase, and having included therein a proportion of sodium butyl sulphonate 17. An improved non-spattering margarine emulsionhaving an oleaginous phase and an aqueous phase and having included therein a proportion of acompound having the formula (la-He -ox in which X stands for an innocuous cation.

18. An emulsion having an oleaginous phase and an aqueous phase and having included therein a proportion of an emulsifying agent comprising a chemical substance characterized by a coaction in its molecule of balanced lipophile and hydrophile groups and represented by the formula in which R is a lipophile radical comprising an ester group, 5 represents sulphur linked to carbon, 0 stands for oxy en, X stands for innocuous cations, and w is asmall whole number, the molecule being devoid of carboxylic groups.

19. An emulsion having an oleaginous phase and an aqueous phase and having included therein a proportion ofan emulsifying agent comprising an ester of sulphoacetic acid, wherein the sulphonic group is balanced by a lipophile group, and wherein the lipoou s. 20. An emulsion having an oleaginous phase and an aqueous phase and having included therein a proportion of an emulsifying agent comprising an ester of sulphoacetic acid, wherein the sulphonic group is balanced by a lipophile group, and wherein the lipophile function is exercised primarily by at least one stearyl group. I

21. An emulsion having an oleaginous phase and an aqueous phase and having included therein a proportion of an emulsifying agent comprising a salt of monostearine sulphoacetate.

22. An emulsion having an oleaginous phase and an aqueous phase, and having included therein a proportion of an emulsifying agent comprising a carboxylic ester of sulphoacetic acid, having balanced lipophile and hydrophile groups, said ester being substantially insoluble in oleaginous and aqueous media, substantially non-volatile at water phile function is exercised primarily by acyl ing a chemical substance characterized by a coaction in its molecule of balanced lipophile and hydrophile groups and represented by the structure in which R is a lipophile radical comprising an ester group and having more than 18 carbon atoms, S represents sulphur linked to carbon, 0 stands for oxygen, X stands for innocuous cations, and w is a small whole number.

2!. An improved emulsion including edible oleaginous material, aqueous material and a proportion of a carboxylic ester of sulphoacetic acid, wherein the hydrophile function is furnished by the sulphonic group, which is balanced by a lipophile group.

26. An improved emulsion including edible oleaginous material, aqueous material, and a proportion of an ester of sulphoaeetic acid, wherein the sulphonic group is balanced by a lipophile group, and wherein the lipophile function is exercised prinr'arily by acyl groups. v

27. An improved emulsion including edible oleaginous material, aqueous material, and a proportion of an ester of sulphoacetic acid, wherein the sulphonic group is balanced by a lipophile group, and wherein the lipophile function is exercised primarily by at least one stearyl group.

28. An improved margarine emulsion including an oleaginous material and aqueous material, and having included therein a proportlon of an lmproving agent comprising palmityl sulphonic acid.

29. An improved margarine emulsion including an oleaginous material and aqueous material and having included therein a proportion of an improving agent comprising the sodium salt of palmityl sulphonic acid.

In witness whereof, I hereunto subscribe my name this 26th day ofSeptember, 1931.

BENJAMIN R. HARRIS. 

